González was first elected to the House of Representatives in a special election held on February 24, 2002, to fill the vacancy left by former House Speaker Edison Misla Aldarondo, after his resignation as Representative from San Juan's 4th District. She was the first female elected representative of San Juan's Fourth District, the youngest member of the 14th Legislative Assembly, and the youngest woman ever to be elected to the Puerto Rico Legislative Assembly. Before being elected as Representative, González served as Chairwoman of the San Juan New Progressive Party Youth Organization and was very active in the Pro-Statehood Students movement while attending college.

González was re-elected in the 2004 Puerto Rico general elections, this time as an At-Large Representative. She served as Chairwoman of the House Government Affairs Committee, and as ranking member of the Budget, San Juan Development, Women's Affairs, and Internal Affairs Committees, as well as the Joint Commission for the Revision of the Civil Code of Puerto Rico.

González was re-elected for another term at the 2008 Puerto Rico general elections obtaining the most votes from her party, and the second most votes overall.[8] At the age of 32, she was elected House Speaker by members of her New Party for Progress delegation during a caucus held on November 7, 2008. González defeated incumbent House Speaker José Aponte Hernández in his bid for re-election to that post, becoming the youngest person in Puerto Rican history to be elected Speaker of the House, and the third woman to hold that seat.

In 2012, González was again re-elected this time gathering the most votes overall, despite the fact that her party lost the majority of seats.[11] The same night of the election, she was selected as Minority Leader of her party.[12]

On September 14, 2015, González announced that she was throwing her hat in the ring to succeed Pedro Pierluisi as Resident Commissioner of Puerto Rico. Six days later, one of Pierluisi's rivals for the gubernatorial nomination, Ricardo Rosselló, chose her as his running mate for June 5, 2016, primary and the November 8, 2016, general election. During the ten months the primary race lasted, various public opinion polls consistently showed González to have over 70% approval ratings of the electorate, making her the most popular politician of any political party on the Island.[citation needed]

On June 5, 2016 González won the NPP primary by a landslide margin of 70.54% of the vote[13] over her opponent Carlos Pesquera. She thus became the first woman in the history of the New Progressive Party to be nominated to the Resident Commissioner seat in Congress for the November general election.